Beta-bromo-ethyl aryl thio-ethers



United States Patent Ofice 3,388,l67 Patented June 11, 1968 3,388,167 B-BRUMfl-ETHYL ARYL THiO-ETHERS Shuichi lshida, Omiya, and Shigeki Kirihara and Shiniehi Usukura, Tokyo, Japan, assignors to Nippon Kayaku Kabushiki Kaisha, Tokyo, Japan, a corporation of Japan No Drawing. Continuation-impart of application Ser. No. 383,901, July 20, 1964. This application Mar. 8, 1965, Ser. No. 438,931

Claims priority, application Japan, July 23, 1963, Pitt/37,185; May 15, 1964-, 39/27,231; June 16, 1964, $963,736

9 Claims. (Cl. 260-609) ABSTRACT OF THE DISCLOSURE Ringsubstituted ,B-bromo-ethyl aryl thio-ethers of the formula R-SCH CH Br wherein R represents phenyl monosubstituted by alkoxy, alkoxycarbonyl, nitro, formyl or, in the or m-position relative to the SCH CH -Br group, by alkyl or a halogen atom; disubstituted phenyl substituted by two of the following: halogen, alkyl or alkoxy groups; aor fi-naphthyl which is unsubstituted or monosubstituted by a halogen atom, the nitro or formyl group or by aikyl, alkoxy or alkoxycarbonyl; or disubstitutcd aor fi-naphthyl having the two substituents selected from the following: halogen, alkyl or alkoxy radicals; are very eiiective in combatting noxious Acarinae, such as spider mites and the like and their stages of development and thus are well suited as acaricides. Methods of preparation and use of the acaricidal compounds are disclosed.

This application is a continuation-impart of our copending application Ser. No. 383,901, filed July 20, 1964 (now abandoned).

This invention relates to new aromatic-aliphatic thioothers which are useful as active ingredients for the combatting of Acarinae and their stages of development.

A number of aromatic-aliphatic thio-ethers which are halogenated in the aliphatic side chain have been known as insecticides, in particular for the control of aphids. Such compounds are, e.g., certain halogeno-alkyl-phenyl sulfides, thio-cresols and tolyl-alkyl-thio-ethers. Insecticides, and especially aphicides are generally not effective against Acarinae.

It is known that plant parasitic spider mites of the Tetranychidae family cause much damage to apple, orange, pear, cherry, cucumber and carnation plantations and the like. Therefore, numerous acaricidal compounds for combatting these spider mites have been in use already. However, these pests quickly develop resistance against the usually employed acaricidal agents so that a decrease in the action of the conventionally applied agents is unavoidable. For practical purposes it is, therefore, important to avoid the development of resistant strains of mites and to find new acaricides against which no resistance has yet developed, and which in particular destroy the eggs of these spider mites.

It has now been found that, surprisingly, new ringsubstituted fi-bromo-ethyl aryl thio-ethers of the formula wherein R represents phenyl monosubstituted by alkoxy, alkoxycarbonyl, nitro, formyl or, in the 0- or m-position, relative to the SCH --CH Br group, by alkyl or a halogen atom; disubstituted phenyl substituted by two of the following: halogen, alkyl or alkoxy groups; aor fl-naphthyl which is unsubstituted or monosubstituted by a halogen atom, the nitro or formyl group or by alkyl,

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alkoxy or alkoxycarbonyl; or disubstituted aor B-naphthyl having the two substituents selected from the following: halogen, alkyl or alkoxy radicals; are very eifective in combatting noxious Acarinae, such as spider mites and the like and their stages of development and thus are well suited as acaricides. These new agents have a special importance for the protection of plants against infestation with noxious Acarinae, and meet especially well the abovedescribed requirements for an effective control of parasitic spider mites in fruit groves and the like plantations. The active agents according to the invention have a particularly good action on the eggs of spider mites. Moreover, they have a peculiar ovicidal eflect in that not only the laid eggs but also the eggs in the body of the female adults are killed, so that eggs laid :by the treated female adults cannot hatch.

Since mites and mite eggs generally occur at the same time, it is often advantageous to use the agents of the invention in mixture with other acaricidally active ingredients such as alkyl 4,4-dichlorobenzilates which have a special effect on the adult stages. They can also be mixed with fungicides.

Especially preferred active agents of the general Formula I are those in which R is a phenyl radical which is monosubstituted in the 0- or m-position; preferred substituents in the aforesaid positions are in particular Cl, CH and -COOCH Preferred substituents of the aromatic radical R when the latter is mono-substituted, are in particular the following: alkyl radicals of l to 4 carbon atoms such as the methyl group, chlorine, fluorine, and bromine, alkoxy radicals of 1 to 4 carbon atoms, especially the methoxy group, alkoxy-carbonyl radicals of 2 to 5 carbon atoms, nitro and formyl. When the aromatic radical R is disubstituted, halogen atoms, in particular chlorine, alkyl of 1 to 4 carbon atoms, and alkoxy of l to 4 carbon atoms, in particular the methyl ethyl and methoxy group are the most effective substituents, the two substituents at R being either identical or differing from each other.

The new acaricidal compounds of Formula I are prepared by reacting a correspondingly substituted thiophenol or thio-naphthol with a 1,2-ethylene halogenohydrin, preferably with ethylene chloro-hydrin or ethylene bromo-hydrin, in the presence of an acid acceptor such as sodium hydroxide, an alkali metal alcoholate such as sodium methylate or a tertiary organic base such as triethyl amine, as well as in the presence of an inert solvent. Solvents suitable for use in the preparation of the compounds of Formula I are water or organic solvents having boiling points in the range of 0 to C. The B-hydroxy-ethyl phenyl-ether or fl-hydroxy-ethyl naphthyl-ether obtained in this way is converted with a brominating agent such as phosphorus tribromide, in an organic solvent and in the presence of an organic base, to form the final product of Formula I. This reaction takes place preferably at a temperature between 0 and 25 C.

According to a modification of this process, the new acaricidal compounds of Formula I can also be prepared by reacting a substituted thio-phenol or thio-naphthol in an organic solvent, such as benzene, chlorobenzene and the like, at a temperature between 50 and 200 C. with ethylene oxide and brominating the resulting hydroxyethyl phenyl-sulfides or hydroxy-ethyl naphthyl-sulfides as described hereinbefore.

Finally, the new compounds of Formula I can be obtained by reacting a substituted thio-phenol or thionaphthol directly with an excess of 1,2-dibrorno-ethane in an organic solvent and preferably in the presence of a base such as sodium methylate or sodium ethylate, at a temperature between 20 and 150 C. Acaricidal compositions containing the new thio-ethers according to the invention are prepared by thorough mixing and grinding of an active compound of Formula I with suitable carrier substances, optionally with the addition of adhesives, or dispersants or solvents. These compositions can be prepared in solid form as dusting powders or scattering agents; or in the form of concentrates of the active ingredients, which can be dispersed in water, such as wettable powders, pastes or emulsions; or in liquid form as solutions, or in formulations suitable for spraying as aerosols, mists, or as fumigation agents.

The invention is further illustrated by the following non-limitative examples in which temperatures are given in degrees centigrade, and parts and percentages are given by weight unless expressly stated otherwise. The relationship between parts by weight and parts by volume is that of grams (g) to milliliters (ml.).

EXAMPLE 1 (a) m-Thiocresol Similar to the method described in Org. Synth. 27, 81, a solution of 126 parts of sodium xanthatc, prepared by mixing at temperatures below 40 C., CS with alcoholic NaOH solution, in 180 parts of water is reacted at 4045 C. with the cold diazonium solution of m-toluidine. The oily rn-tOlyl ethyl xanthate so obtained is separated and dissolved in ethanol. To the boiling alcoholic xanthate solution sodium hydroxide pellets are added and the major part of the alcohol is distilled off. The residue is taken up in water and the aqueous solution is made strongly acid to Congo red paper using 6 N sulfuric acid and after addition of zinc dust the m-thiocresol is distilled with steam.

(b) 2-(m-Tolylthio)-ethanol 31.5 parts m-thiocresol were dissolved into the solution prepared from 18.5 parts of KOH and 70 parts by volume of water. To this solution were added 21 parts of ethylene chlorohydrin at 70, then the reaction mixture was reacted 1.5 hours at 90. The product was extracted with benzene and distilled at 126 C./1 torr.

20 parts phosphorus tribromide in 15 parts by volume of benzene were mixed with 2.7 parts pyridine under cooling in an ice bath. To this solution was added during 1 hour at to 0 a mixture of 34.5 parts of S-Z-hydroxyethyl-S-m-tolylsulfide and 1.4 parts of pyridine. The reaction mixture was stirred 1 hour with cooling as above and then allowed to stand at room temperature. The reaction mixture was treated with ice water containing hydrochloric acid and extracted with benzene. The benzene was then distilled off and the S-fl-bromoethyl-S-m-tolylsulfide removed by distillation at 1-12-l14/1.5 torr.

EXAMPLE 2 A solution of 500 parts of m-thio-cresol and 218 parts of sodium methylate (about 4 mols each) in 1000 parts by volume of ethanol is poured into a mixture of 2300 parts -(12.2 mols) of ethylene bromide and 1500 parts by volume of ethanol, while cooling with a mixture of ice and saturated sodium chloride solution to a temperature of to 17.

After completion of the reaction, the major portion of the solvent is distilled oil in vacuo, the residue is mixed with water and the oily phase, which separates, is dissolved in ether. The ether solution is washed with water and dried with sodium sulfate; the ether is distilled off in vacuo and the residue fractionated in high vacuum.

The fraction boiling at 88/0.04 torr is collected. It consists of S-B-bromoethyl-S-3-methylphenyl-sulfide.

The following acaricidally active compounds are produced from the correspondingly substituted starting materials by the procedure given in the above examples:

Sfi-bromoethyl-S-Z-chloro-phenylsulfide S-p-bromoethyl-S-3-chloro-phenyl-sulfide S-fl-bromoethyl-S-3 -methoxycarbonyl-phenylsulfide S-fl-bromoethyl-S-3 -methoxy-phenyl-sulfide S-fl-bromoethyl-S-El -ch1oro-4-methoxy-phenyl-sulfide S-fi-b romoethyl-S-3 -methyl-phenyl-sulfide S-fl-bromoethyl-S-3,4-di-methyl-phenyl-sulfide S-B-bromoethyl-S-methyl-4-methoxy-phenyl'sulfide S-fi-bromoethyl-S-2-methoxycarbonyl-phcnyl-sulfide S-,6-b rom oeth yl-S-Z-chlorophenyl-sulfide S-fl-bromoethyl-S-2,5-dichloro-phenyl-sulfide S-/3-bromoethyl-S2-methyl-phenyl-sulfide S-e-b romoethyl-S-2-methyl-5-isopropyl-phenyl-sul lidc S-fl-bromoethyl-S-2-methyl-4-methoxy-phenyl-sulfide S-fi-bromoethyl-S-2-methoxy-phenyl-sulfide S-fl-bromoethyl-S-Z,4-di-methoxy-phenyl-sulfide S-fi-bromoethyl-S-2,5-di-methoxy-phenyl-sulfide S-{i-bromoethyl-S-Z-methoxy-5-chloro-phenyl-sulfi de S-[i-bromoethyLS-3 -ethoxycarbonyl-phenyl-sulfide S-t3-b.romoethyl-S-isopropoxycarbonyl-phenyl-sulfide S,8bromoethyl-S-4-nitrophenyl-sulfide S-p-bromoethyl-S-3 -nitrophenyl-sulfide S-[i-bromoethyl-S-2-nitrophenyl-sulfide S-fi-bromoethyl-S-4-methoxycarbonyl-phenyl-sulfide S-fl-bromoethyl-S-4-mcthoxy-phenyl-sulfide S-B-bromoethyl-S-3 -methyl-6-methoxy-phenyl-sulfide S-{i-b rom oethyl-S-2-chloro-S-methyl-phenyl-sulfide S-fl-bromoethyl-SG-n-propoxycarbonyl-phenyl-sulfide S-fi-bromoethyl-S-3 -n-butoxycarbouyl-phenyl-sulfide S-,8-bromoethyl-S-1-naphthyl-sulfide -/3-bromoeth yl-S-Z-napthyl-sulfide ,3-bromoethyl-S-4-formyl-phenyl-sulfide ,8-bromoethyl-S-3 -bromo-phenyl-sulfide p-bro1noethyl-S-4-chlorol-naphthyl-sulfide fl-bromoethyl-S-2-chloro-1-naphthyl-sulfide fi-bromoethyl-S- t-nitro- 1 -naphthyl-sulfide S-fl-bromoethylS-6,8-dinitro-1 -naphthyl-sulfide S-,8-bromoethyl-S- 1 -ethoxy-2-n aphth yl-sulfide S-p-bromocthyl-S-3 -methoxycarbonyl-2-naphthylsulfide S-B-b romoethyl-S-2,4-dibromol-naphthyl-sulfi de The thiophenols used as starting materials in the production of these compounds are prepared as described in Org. Synth. [viz. Example 1 step (21)] from the corresponding well-known starting materials.

The invention is further illustrated by the following nonlimitative examples. Parts are given therein as parts by Weight and temperatures by Centigrade.

S S S S S S EXAMPLE 3 Emulsifiable solution: Parts 2-bromoethyl-m-tolyl-sulfide 50 Xylene 10 Isopropyl alcohol 50 Polyoxyethylene alkylphenol 25 The above chemicals are mixed to form an emulsifiable solution which is diluted wtih Water for use as an acaricidal spray.

EXAMPLE 4 Wettable powder: Parts 2-bromoethyl-m-tolyl-sulfide 20 Diatomaceous earth 20 Dehydrated silicicacid 10 Mixture of bentonite and kaoline:

Weight ratio 1:1 45

Mixture of:

Sodium lignin sulfonate, sodium dibutyl-naphthalene sulfonate, weight ratio 1:1:1 5

The above chemicals are mixed and crushed to form fine powder which is diluted with water for use as acaricide.

EXAMPLE 5 Dusting powder: Parts 2-bromoethyl-m-tolyl-sulfide 5 Talcum The above chemicals are mixed and crushed to form a fine powder, ready for use as acaricide.

EXAMPLE 6 Wettable powders 25 parts of S-B-bromoethyl-S-3-chloro-phenyl-sulfide are mixed and ground with 5 parts of sulfated hexadecyl glycol ether and 2.5 parts of a dispersant consisting of the condensation product of naphthalene sulfonic acid and formaldehyde and 67.5 parts of neutral sodium aluminium silicate. The 25% Wettable powder obtained has good suspensibility and low foam formation.

Such Wettable powders can be diluted with water to form suspensions with a concentration of 0.1 to 1% active substance. These suspensions are used to combat mites and their stages of development on vegetables and ornamentals.

EXAMPLE 7 Emulsion concentrates 5 parts of 4,4'-dichlorobenzilic-acid-isopropyl ester, 5 parts of 4,4-dichlorobenzilic-acid-ethyl ester, and parts of S-B-bromoethyl-S-3-methoxy-phenyl-sulfide are dissolved in 60 parts of xylene and 20 parts of nonyl phenyl polyglycol ether containing an average of ether oxygen atoms as emulsifying agent. An emulsifiable solution is obtained which can be diluted with water to any concentration desired. The diluted agent serves for combating acaricides, for instance in fruit groves.

EXAMPLE 8 Emulsion concentrates 10 parts of S-B-bromoethyl-S-l-naphthyl-sulfide are mixed with/or dissolved in parts of xylene, 20 parts of ethyl acetate, parts of acetone and 20 parts of nonylphenyl polyethylene glycol ether (about 15 mols of ethylene oxide per mol of nonylphenol) as emulsifying agent. A 10% emulsion concentrate is obtained which can be diluted with water to any concentration desired. These emulsions are used to combat mites on plums and roses.

EXAMPLE 9 Emulsifiable solution: Parts 2-bromoethy1-3-chlorophenyl sulfide 30 Xylene 10 Isopropyl alcohol Polyoxyethylene alkylphenol 25 The above chemicals are mixed to form an emulsifiable solution which is diluted with water for spraying.

Sodium lignin sulfonate, sodium dibutyl naphthalene sulfonate 1 1 Mixture of the same weight of each.

The above chemicals are mixed and crushed to form fine powder which is diluted with water for use.

EXAMPLE 11 Dusting powder: Parts 2-bromoethyl-2-chlorophenyl sulfide 2.5 2-bromoethyl-3-chlorophenyl sulfide 2.5 Talc 95 The above chemicals are mixed and crushed to form fine powder which is applied as it is for use.

6 EXAMPLE 12 Emulsifiable solution: Parts 2-bromoethyl 3 methoxycarbonylphenyl sulfide 30 Xylene l0 Isopropyl alcohol 35 Polyoxyethylene alkylphenol 25 The above chemicals are mixed to form an emulsifiable solution which is diluted with water for spraying.

EXAMPLE 13 Wettable powder: Parts 2-bromoethyl-3,4-dimethylphenyl sulfide 2O Diatomaceous earth 20 Dehydrated silicic acid 10 Bentonite, kaoline 1 45 Sodium ligninsulfonate, sodium dibutylnaphthalene sulfonate 2 5 1 Mixture of the same weight of each. 2 Mixture of equal amounts of each.

The above chemicals are mixed and crushed to form fine powder which is diluted with water for use.

EXAMPLE 14 Dusting powder: Parts 2-bromoethyl-3-ethoxycarbonylphenyl sulfide 3 Mixture of talc and kaolinc 97 The above chemicals are mixed and crushed to form fine powder which is applied as it is for use.

The eflicacy of compounds according to the invention as acaricides is shown in the following experiments:

Experiment I TABLE 1 Tctranychus telarius L.

Mortality of Mortality of adults, percent eggs, percent Cono. (percent):

A series of test solutions were prepared by diluting the solution of Example 3 with water sutficiently to obtain the concentrations given in the first column of the table.

Experiment II 2-bromoethyl-4-chlorophenyl sulfide, an isomer of the above-mentioned 2-chloro and 3-chloro-phenyl sulfides, is well-known, and experiments were previously made against Aphis fabae and Macrosiphum pisi, but did not go beyond preceiving its phytotoxicity to plants. (Chemical Abstracts: Vol. 53, p. 7493, 1959.)

The unexpectedly very satisfactory acaricidal ovicidal etfect of the two Z-chloro and 3-chlo1'o compounds of this invention and the unpromising effect of the abovementioned known 4-chloro compound which was only equal to that of the 3-chloro compound in more than 10 0 times the concentration of the latter are shown in the following experiment:

The first leaves (2 leaves), cut into squares of 2.5 cm. by 2.5 cm. of the French dwarf bean (variety: Top Crop) grown in a pot of 6 cm. diameter were infested with six to eight female adults of T etranychus tclarius L.

After two days of oviposition, the adults were removed and the eggs were counted. The leaves were then dipped into the test solution for 10 seconds. The unhatched eggs 5 were counted through a binocular microscope after leaving in a plastic covered house for 6-8 days after treating, that is, after hatching of the mites on the untreated leaves.

TABLE 2.OVICIDAL EFFECT OF 2-BROMOETHYL CHLO' Experiment III Test against eggs of Tetranychus telarius L.The first leaves (2 leaves) out into squares (2.5 cm? of the French dwarf bean (variety: Top Crop) grown in a pot of 6 cm. diameter were infested with 6-8 female adults of Tetranychus telarius L. After two days oviposition, the adults were removed and the eggs were counted. Then the leaves were dipped into the test solution for 10 seconds. The unhatched eggs were counted through a binocular microscope in six to eight days after the treatment and having grown in the vinyl house, that is, after hatching of the control.

8 Experiment V Test against female adults of T ctranyclzus telarius L.The leaves of French dwarf bean, prepared in the same way as in Experiment III, were infested with ten female adults. After the mites became stationary, the leaves were dipped into the test solution for ten seconds. After two days the survivors and the dead were counted.

TABLE 5 Mortality (percent) Compound (00110.) 0.1% 0.05% 0.0259,?

2-bromoethyl-l-nitrophenyl sulfide... 2-bromoethyl-3-methoxyphenyl sulfi 2-bromoethyl-2-nitrophenyl sulfide.

2-bromoethyl-2-1ncthoxyphenyl sulfi 100. 0 100.0 2-bron1oethyl-a-naphthyl sulfide I00. 0 100. 0 100. 0 2-bromoethyl-fi-naphthyl sulfide 100. 0 92. 0 80. 0 2-bromoetl1yl-4-methoxypl1enyl sulfide 100. 0

As shown in the above, the compounds of this invention are very ovicidal as well as acaricidal, and moreover have the peculiar property that the eggs laid by the treated female adults do not hatch. Therefore the compounds of this invention can prevent the mites from multiplying.

The acaricidally active compounds of this invention can be used as miticides for agricultural and horticultural use by mixing one or several of them with carriers, i.e. agents inert to the said active compounds and serving only to convey them to their destination.

Furthermore these compounds can be made into far stronger miticides which kill adults and larvae as Well as eggs by using them in combination with another compound of acaricidal property.

More particularly, by mixing a compound of this invention as active ingredient with other compounds which are active especially against adults of mites and formulating the mixture into emulsifiable solution, dusting powder, or

TABLE 3 Unhatehed Eggs (Percent) Compound (Cone) 0.1% 0.05% o. 025% 0.0125% 0.00625% 0.003125% 2-bromoethyli-formylphenyl sulfide Q7 82 93 2-bron1oetl1yl-4-nitrophenyl sulfide 100 93 100 100 91 66 2-bromoethyl-3-methoxycarbonylphenyl sulfide 82 87 98 97 S14 2-bromoethyl-3 methoxyphenyl sulfide. 92 94 S8 94 81 87 2-bromoethyl-2-methoxycarbonylphenyl sulfide 98 80 96 89 87 2-brornoethyl-lmethoxyphenyl sulfide 100 2 brornoethyl-3-ethoxycarbonylphenyl sulfide- 2-brornoethyl-3-isopropoxycarbonylphenyl sulfido 2 bromoethyl-3-n-propoxycarbonylphenyl sulfide 2-bromoethyl-3-n-butoxycarbonylphenyl sulfide. 2-bromoethyl4-methoxycarbonylphenyl sulfide- 2-bromoethyl-3-methyl-6methoxyphen yl sulfide 2-bromoethyl-3,4-di1nethylphenyl sulfide 2-bromoethyl-2-methyl4-methoxyphenyl sulfide. 2-bromoethyl-2,4-dimethoxy-phenyl sulfide Z-bromOethyI-Q-naphthyl sulfide 2-bromoethyl-B-naphthyl sulfide Experiment IV Test against eggs in the body of T etranychus telarius L.--The leaves of the French dwarf bean, prepared in the same way as in Experiment III, were infested with ten female adults.

After the mites became stationary, the leaves were dipped into the test solution for 10 seconds. After two days the survivors were removed and the eggs were counted, and after an additional seven days the unhatched 6r eggs were counted.

TABLE 4 Cone. Eggs Eggs un- (pereent) laid hatched Percent Compound active ingredient of active after after of eggs ingredient 2 days further unhatched 7 days 2-bromoethyl-S-methoxycarbonylphenyl 0. 04 38 36 94. 7 sulfide. 0. 02 57 56 98. 2 0.01 45 45 100.0 Control treated with water 129 l 0. s

(b) mono-substituted phenyl having one of the following substituents in one of the positions ortho and meta to SCH -CH Br as follows: halogen, alkoxy of from 1 to 4 carbon atoms and alkyl of from 1 to 4 carbon atoms,

(c) unsubstituted naphthyl,

(d) mono-substituted naphthyl substituted with one of the following substituents: halogen, nitro, formyl, alkyl of from 1 to 4 carbon atoms, alkoxy of from 1 to 4 carbon atoms, alkoxy-carbonyl of from 2 to 5 carbon atoms, and

(e) disubstituted naphthyl substituted with two of the following substituents: halogen, lower alkyl, lower alkoxy, halogen being throughout selected from the group consisting of F, Cl and Br.

2. S-B bromoethyl-S-2-chlorophenyl-sulfide.

3. S-B-bromoethyl-S-2-methyl-phenyl-sulfide.

4. S-B-bromoethyl-S-Z-methoxy-phenyl-su1fide.

5. S-fl-bromoethyl-S-3-chloro-phenyl-sulfide.

References Cited Greenwood et al., J. Chem. Soc. (1953), pp. 1514- CHARLES B. PARKER, Primary Examiner.

J. P. BRUST, Examiner.

D. R. PHILLIPS, Assistant Examiner. 

